CN101974803B - Vapor-grown carbon fiber, production method thereof and composite material containing the same - Google Patents

Vapor-grown carbon fiber, production method thereof and composite material containing the same Download PDF

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Publication number
CN101974803B
CN101974803B CN2010105419545A CN201010541954A CN101974803B CN 101974803 B CN101974803 B CN 101974803B CN 2010105419545 A CN2010105419545 A CN 2010105419545A CN 201010541954 A CN201010541954 A CN 201010541954A CN 101974803 B CN101974803 B CN 101974803B
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carbon fiber
phase growth
vapor phase
carbon
fiber
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CN101974803A (en
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矢野幸太郎
山本龙之
森田利夫
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Resonac Holdings Corp
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Showa Denko KK
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/754—Dendrimer, i.e. serially branching or "tree-like" structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
    • Y10S977/833—Thermal property of nanomaterial, e.g. thermally conducting/insulating or exhibiting peltier or seebeck effect
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Abstract

The invention relates to a vapor-grown carbon fiber having a diameter ratio of 100 to 200 and a bulk density of 0.02 g/cm<3> or less, wherein filaments having a diameter within the mean fiber diameter plus/minus 20 % occupies 65 % or more (on a number basis). The production method thereof comprises the steps of: mixing carrier gas with raw-material gas containing carbon source and transition metal compound, leading the quantity of the carrier to be 1-100mol based on 1 mol organic compound of the carbon source, and sending the gas mixture into a reactor.

Description

The carbon fiber of vapor phase growth, its preparation method and comprise the composite of this carbon fiber
The application is that application number is dividing an application of 200580018735.6 application for a patent for invention, and the applying date of original application is on June 7th, 2005, and denomination of invention is " carbon fiber of vapor phase growth, its preparation method and comprise the composite of this carbon fiber ".
The cross reference of related application
The application is the application of submitting by 35U.S.C.Section 111 (a); Regulation according to 35U.S.C.Section 119 (e) (1) requires the U.S. Provisional Application No.60/578 that submitted on June 14th, 2004 that is specified in by 35U.S.C.111 (b); 850 and the U.S. Provisional Application No.60/607 that submits on September 8th, 2004,597 right.
Technical field
The present invention relates to the carbon fiber of vapor phase growth.More specifically; The present invention relates to when being used to prepare composite in the base material that it is dispersed in resin for example; Even the carbon fiber consumption that its consumption is a conventional gas-phase grows is half the or lower, still show the carbon fiber of the vapor phase growth of the suitable performance of carbon fiber of growing with conventional gas-phase; Also relate to method for preparing this carbon fiber and the composite that comprises this carbon fiber.
Background technology
Carbon fiber being dispersed in the base material of resin for example is a technology that electric conductivity for example or thermal conductivity are provided extensively commonly used.Add under the situation of resin at carbon fiber vapor phase growth; Even addition is less; So that the mold pressing ability of gained resin combination and the outward appearance of mechanograph are not had negative effect; But the electric conductivity of resin combination and thermal conductivity still can obviously be improved (Japan Patent No.2862578, WO 91/03057).
Generally speaking, the carbon fiber of vapor phase growth is being added under the situation of resin etc., the draw ratio of carbon fiber is big more, and the performance of giving electric conductivity and thermal conductivity is high more.Carbon fiber (VGCF, the registration mark of the vapor phase growth that current commerce can get; The product of Showa Denko K.K.) has fiber diameter, about 45 the draw ratio of about 150nm and be as short as the fibre length of about 6.7 μ m.
As the instance that has than the carbon fiber of long fiber length, Japan Patent No.1701869 (WO86/03455) has described has 100 or the carbon fiber of high length-diameter ratio more.Yet this carbon fiber has the fubril diameter of 3.5-70nm, and specific area is big, and surface energy is high, so there is following problem in carbon fiber: this carbon fiber usually forms aggregation; This carbon fiber is difficult to be dispersed in the resin; The composite demonstration that comprises this carbon fiber thus can't gratifying characteristic, for example electric conductivity.
Summary of the invention
The object of the present invention is to provide a kind of carbon fiber, wherein when with this carbon fiber with the base material of comparing the amount that will lack with the situation of the carbon fiber of conventional gas-phase growth and adding resin for example in the time, this carbon fiber can be given its excellent electric conductivity and thermal conductivity.Another purpose provides the method that is used to prepare carbon fiber.
The inventor has summarized carbon source and has carried out the reaction condition that thermal decomposition prepares gas-phase growth of carbon fibre; And have been found that; In the time will comprising carbon source and be sprayed onto the inwall of reactor as the even gaseous mixture of the transistion metal compound of catalyst, the carbon fiber that makes has specific fibre diameter and specific draw ratio; Find that also when the carbon fiber that will prepare thus was added in the base material of resin for example with the preparation composite, even the addition of carbon fiber lacks than the situation of the carbon fiber of conventional gas-phase growth, composite still showed excellent electric conductivity and thermal conductivity.The present invention is based on these finds to accomplish.
Therefore, the invention provides a kind of carbon fiber of vapor phase growth, prepare the method and the composite that comprises this carbon fiber of this carbon fiber, summarize as follows:
(1) carbon fiber of vapor phase growth, it has the fiber diameter of 80-500nm and the draw ratio of 100-200, wherein fibre diameter drop on ± carbon fiber wire in the 20% fiber diameter scope accounts for all 65% or more (based on radicals) of carbon fiber.
(2) like the carbon fiber of above (1) described vapor phase growth, it has 0.02g/cm 3Or lower bulk density.
(3) like the carbon fiber of above (1) described vapor phase growth, it has 0.015g/cm 3Or lower bulk density.
(4) like the carbon fiber of any described vapor phase growth in above (1)-(3), it is being compressed to 0.8g/cm 3Bulk density the time, said carbon fiber shows 0.015 Ω cm or lower resistivity.(5) like the carbon fiber of any described vapor phase growth in above (1)-(4), it shows 0.2 or lower Id/Ig, and wherein Id is illustrated in 1341-1360cm in the raman scattering spectrum of carbon fiber -1The peak height of wave band (d line), Ig is illustrated in 1570-1580cm in the said spectrum -1The peak height (Ig) of wave band (g line).
(6) like the carbon fiber of any described vapor phase growth in above (1)-(5), like what record through the X-ray diffraction determination method, the carbon fiber of said vapor phase growth has 0.339nm or lower centre plane spacing (d at (002) mask 002).
(7) like the carbon fiber of any described vapor phase growth in above (1)-(6), its surface is through oxidation processes.
(8) assembled the carbon fiber of the vapor phase growth that forms by any described carbon fiber in above (1)-(7), it has 0.04g/cm 3Or higher bulk density.
(9) method of carbon fiber of preparation vapor phase growth comprises: carbon source is being carried out thermal decomposition under 800-1300 ℃ in the presence of as the transistion metal compound of catalyst; Carbon source and transistion metal compound are sprayed onto on the inwall of reactor with gas form, thereby reaction is carried out, wherein transistion metal compound has 0.13kPa (1mmHg) or higher air pressure under 150 ℃.
(10) like above (9) the described method for preparing gas-phase growth of carbon fibre; Wherein carrier gas is mixed with the unstrpped gas that comprises carbon source and transistion metal compound; Make that the amount of said carrier gas is 1-100mol based on the 1mol organic compound as carbon source, subsequently the gained admixture of gas is sent in the reactor.
(11), wherein 1.3kPa (10mmHg) will under 50 ℃, be had or more anticyclonic sulfur-containing compound is sent into reactor with carbon source and transistion metal compound with gas form like above (9) or (10) the described method for preparing gas-phase growth of carbon fibre.
(12) like above (9) the described method for preparing gas-phase growth of carbon fibre, the solution that wherein will comprise carbon source, transistion metal compound and sulfur-containing compound is heated to 200-700 ℃, thereby with vaporizer; The gained gasification product is mixed with carrier gas; And the gained admixture of gas is sprayed onto its temperature adjusted to the inwall of 800-1300 ℃ reactor.
(13) by the carbon fiber of the vapor phase growth of the carbon fiber preparation method of any described vapor phase growth in above (9)-(12) preparation; The carbon fiber of said vapor phase growth has the fiber diameter of 80-500nm and the draw ratio of 100-200, wherein fibre diameter drop on ± carbon fiber wire in the 20% fiber diameter scope accounts for all 65% or more (based on radicals) of carbon fiber.
(14) a kind of composite comprises the carbon fiber of any described vapor phase growth in the base material that is selected from resin, metal and ceramic material and above (1)-(8) and (13), and the carbon fiber of said vapor phase growth is dispersed in the base material.
Description of drawings
Fig. 1 representes the preparation method's of gas-phase growth of carbon fibre of the present invention equipment flowsheet.
Fig. 2 is the figure that is illustrated in the specific insulation of the composite of preparation in embodiment 2 and the Comparative Examples 2, and specific insulation records through four probe method.
Fig. 3 is illustrated in the fiber diameter distribution profile of the carbon fiber of preparation among the embodiment 1.
Fig. 4 is illustrated in the fiber diameter distribution profile of the carbon fiber of preparation in the Comparative Examples 1.
Fig. 5 is illustrated in the fiber diameter distribution profile of the carbon fiber of preparation among the embodiment 4.
The specific embodiment
The carbon fiber of vapor phase growth of the present invention has 80-500nm, preferred 80-140nm, the more preferably fiber diameter of 80-110nm.The variation in fiber diameter of the silk of this carbon fiber is little; And fibre diameter drops on ± and carbon fiber wire in the 20% fiber diameter scope accounts for all 65% (based on radicals) of silk or higher of carbon fiber; Preferably account for 70% (based on radical) or higher, more preferably account for 75% (based on radical) or higher." fibre diameter drops on ± carbon fiber wire in the 20% fiber diameter scope account for all 65% (based on radicals) of silk or higher of carbon fiber " refers to this situation: for example; When fiber diameter is 100nm, fibre diameter be the carbon fiber wire of 80-120nm account for carbon fiber whole filametntary 65% or higher.
Carbon fiber of the present invention with above-mentioned characteristic has the average aspect ratio of 100-200.
The carbon fiber of vapor phase growth of the present invention preferably has 0.02g/cm 3Or lower, more preferably 0.015g/cm 3Or lower bulk density.When bulk density surpasses 0.02g/cm 3The time, be about 3 quality % even add the amount of the carbon fiber in the resin to, almost do not observe electric conductivity enhancing in the gained composite in some cases.Simultaneously, when the bulk density of carbon fiber is crossed when low, the productive rate reduction of the composite that carbon fiber and resin form.Therefore, the bulk density of carbon fiber is preferably 0.005g/cm 3Or it is higher.
In order to improve the reappearance that bulk density is measured, the bulk density of carbon fiber obtains through following process: the carbon fiber of preparation was heated 15 minutes in argon atmospher under 1000 ℃; The carbon fiber that uses blender (MX-X62, the product of Matsushita Electric Industrial Co.Ltd) to heat was thus milled 1 minute; With grind thus carbon fiber place and measure cylinder, use vibrator (Touch Mixer MT-31, Yamato Scientific Co., the product of Ltd) vibration 1 minute then; Subsequently, measure the volume of gained carbon fiber, and calculate the bulk density of carbon fiber.
In the carbon fiber of vapor phase growth of the present invention, preferably, 1341-1360cm in the raman scattering spectrum of carbon fiber -11570-1580cm in the peak height (Id) of wave band (d line) and this spectrum -1The ratio of the peak height (Ig) of wave band (g line), promptly Id/Ig is 0.2 or lower.The Id/Ig ratio is 0.05-0.2 more preferably.When the Id/Ig ratio surpassed 0.2, carbon fiber possibly present poor crystallinity, and the composite of this carbon fiber and resin formation can not show gratifying electric conductivity in some cases thus.
In the carbon fiber of vapor phase growth of the present invention, preferably record like the X-ray diffraction determination method, this carbon fiber has 0.339nm or lower centre plane spacing (d at (002) mask 002).Work as d 002When surpassing 0.339nm, carbon fiber possibly present poor crystallinity, utilizes the composite of this carbon fiber can not show gratifying electric conductivity in some cases thus.
From carbon fiber effectively being sneaked into the viewpoint of resin, preferably, it is high that the bulk density of carbon fiber is wanted.For this reason, frangible carbon fiber formation aggregation is effective.In order to form this aggregation, be to adopt grinding technology, granulating technique or compress technique effectively.The instance of grinding technology comprises and adopts jet mill to handle.The instance of granulating technique is included in the existence of adhesive and adopts the Henschel blender to handle down.The instance of compress technique comprises the wherein compressed product of formation carbon fiber during aforementioned hot is handled, and after heat treatment, adopts the technology of these compressed product of corase grind such as sliding wear (feather mill); Wherein will pass through the compacting machine compression Technique through the carbon fiber of milling and classifying.
Because the carbon fiber aggregate that bulk density increases is frangible in blender is handled, so the blender that the bulk density of this carbon fiber aggregate must not adopt in aforementioned bulk density measuring method is measured under handling.Particularly; Bulk density is through following process measurement: with the heating 15 minutes in argon atmospher under 1000 ℃ of the carbon fiber aggregate of preparation; And the aggregation that will heat thus is placed on and measures in the cylinder, uses vibrator (Touch Mixer MT-31, Yamato Scientific Co. then; Ltd. product) vibration is 1 minute, measures the bulk density of this aggregation again.Bulk density with carbon fiber aggregate of high-bulk-density increases manyly more, and this carbon fiber is compared easier kneading with the carbon fiber that is formed aggregation by it and advanced in the resin.The bulk density of this carbon fiber aggregate is preferably 0.03g/cm 3Or higher, 0.04g/cm more preferably 3Or it is higher.
The carbon fiber of vapor phase growth of the present invention preferably has 0.015 Ω cm or lower resistivity.When resistivity surpasses 0.015 Ω cm, be about 2 quality % even add the amount of the carbon fiber in the resin to, almost do not observe electric conductivity enhancing in the gained composite in some cases.Because resistivity is that the carbon fiber of fine dispersion is measured, so the resistivity value of mentioning is that carbon fiber is compressed to bulk density is 0.8g/cm through measuring here 3The time formed goods resistivity and the value that obtains.The resistivity of carbon fiber is 0.008 Ω cm or lower more preferably.
The carbon fiber of vapor phase growth of the present invention is easy to form network of fibers, and demonstrates excellent dispersiveness.Therefore, only the small amount of carbon fiber is added in the base material of resin for example and just improved electric conductivity and thermal conductivity.
After the carbon fiber that makes through the inventive method formed compressed product, owing to formed strong network of fibers, these goods showed low resistivity.The carbon fiber of vapor phase growth of the present invention has low bulk density, and when assembling the formation fiber block, a little less than its cohesive force, therefore when this carbon fiber mixed with the base material of for example resin, carbon fiber was well dispersed in the base material.
The carbon fiber of vapor phase growth of the present invention shows above-mentioned characteristic, can be through the preparation of following method: with carbon source thermal decomposition in the presence of as the transistion metal compound of catalyst; Particularly, this carbon source and transistion metal compound are sprayed onto the inwall of reactor with gas form, thereby make this carbon source carry out pyrolysis.
Carbon source (organic compound) as carbon fiber material can be any gasifiable organic compound.Yet preferably, carbon source is the organic compound that gasifies at a lower temperature.The instantiation of the carbon source that can adopt comprises aromatic compounds, for example benzene, toluene and xylene; Straight-chain hydrocarbons, for example hexane and heptane; Cyclic hydrocarbon, for example cyclohexane; Alcohol, for example methyl alcohol and ethanol; Gasoline; And kerosene.Wherein, preferably aromatic compounds, most preferably benzene.These carbon sources can be used separately or two kinds or more kinds of material are used in combination.
The organo-metallic compound or the inorganic compound that preferably comprise the 4-10 group 4 transition metal as the transistion metal compound of catalyst.Especially, preferably comprise transition metal, for example the organo-metallic compound of Fe, Ni or Co.
In the present invention, transistion metal compound reacts with gas form.Therefore, employing has anticyclonic transistion metal compound; Particularly, the air pressure of transistion metal compound under 150 ℃ is 133Pa (1mmHg) or higher.The instantiation of this compound comprises ferrocene and dicyclopentadienyl nickel.
The diameter of carbon fiber to be prepared and length, and comprise the amount of particle can be through regulating the concentration of transistion metal compound in the raw material, regulate the amount that carbon fiber forms required catalyst particle thus and control.In order to prepare the carbon fiber with 80nm or higher fibre diameter, the amount of ferrocene is adjusted to based on the preferred prestige 1-5 quality of carbon source total amount %, more preferably 2-4 quality %.When the amount of the catalyst that is adopted surpassed above scope, the fibre diameter of gained carbon fiber excessively reduced, and carbon fiber is for example mediated into the base material of the resin difficulty that becomes.On the contrary, when the amount of the catalyst that is adopted during, generate a large amount of carbon particles less than above scope.
The sulphur source is added raw material can make the productive rate of carbon fiber further improve.The sulphur source can be any gasifiable sulphur compound.Yet preferably, the sulphur source is to have anticyclonic sulphur compound; Particularly, the air pressure of sulphur compound under 50 ℃ is 10mmHg or higher.The instance in this sulphur source includes organic sulfur compound, for example thiophene and inorganic sulfide compound, for example hydrogen sulfide.Particularly, thiophene preferably.These sulphur sources can be used separately or two kinds or the use of more kinds of combinations of substances.
In the present invention, the sulphur source of above-mentioned carbon source, transistion metal compound and inessential component is added reactor with gas form, thereby reaction is carried out.In this case, can gasify respectively in carbon source, transistion metal compound and sulphur source, and can the material that gasify thus be mixed sending into reactor in the past.Yet, preferably, prepare liquid charging stock by carbon source, transistion metal compound and sulphur source, and the material gasification that will make thus, add reactor then.
Unstrpped gas is sprayed onto the inwall of reactor.This spray process is heating raw effectively, and promotes the thermal decomposition of raw material, thereby can be with the little carbon fiber filament of produced in high yields variation in fiber diameter.
Fig. 1 representes the carbon fiber preparation method's of vapor phase growth of the present invention flow chart.
Liquid charging stock (1) is added in the gasifier (3) through liquid charge pump (not shown), thus preparation unstrpped gas.In order to obtain the unstrpped gas of constant composition, preferably with whole liquid charging stock gasifications.Gasifier is heated to uniform temperature, and liquid charging stock can not decompose so that liquid charging stock is gasified totally.Heating-up temperature is preferably 200-700 ℃, more preferably 350-550 ℃.Through with liquid charging stock in nozzle unit is sprayed onto gasifier, this raw material effectively gasifies.In order to control the feed rate of unstrpped gas, can carrier gas (2a) be added gasifier.Yet from the viewpoint of the heater loads that reduces gasifier, preferably, the flow velocity of carrier gas is low as far as possible.
The raw material of gasification is thus mixed with carrier gas (2b) before the thermal response carrying out.Carrier gas preferably comprises reducing gas, hydrogen for example, and when raw material and catalyst are delivered to the pyrolysis zone, use, to induce and to keep the catalytic activity of transition metal.The amount of carrier gas is preferably 1-100mol based on 1.0mol as the organic compound of carbon source.Have in the carbon fiber of good dispersion in preparation, importantly unstrpped gas is being added before the pyrolysis zone (reactor) (5), how it is evenly concentrated.In order to improve the uniformity of raw gas concentration, liquid charging stock must be gasified totally in gasifier, and unstrpped gas and carrier gas must fully mix.From the viewpoint that liquid charging stock is gasified totally, preferably suitably select carbon source, transistion metal compound and sulphur source.And, from unstrpped gas and the well-mixed viewpoint of carrier, preferably adopt static mixer (STP) (agitating device) (4).
When unstrpped gas being sent into reactor (5), unstrpped gas thermal decomposition, thereby preparation carbon fiber.The temperature of inside reactor is adjusted to 800-1300 ℃, preferably is adjusted to 900-1250 ℃.As reactor, can use by the material that can tolerate 1300 ℃ of reaction temperatures, for example the reactor of aluminium oxide, zirconia, magnesia, silicon nitride or carborundum formation.Reactor is preferably designed for tubular type.Tubular reactor (reaction tube) is by being arranged on the outer heater heating of pipe.Through increasing the retention time of raw material in reactor,, thereby improve the productive rate of carbon fiber so that raw material decomposes fully.Particularly, raw material retention time in reactor under 1250 ℃ is 2-10 second, is preferably 4-6 second.
Can use direct carbon fiber, and not need any processing through above-mentioned prepared in reaction.Replacedly, can with carbon fiber in about 800-about 2000 ℃ down heating after therefrom removing impurity, re-use, can with carbon fiber in 2000 ℃ or more the relative superiority or inferiority heating after improving its crystallinity, re-use.
In order to improve the wettability of carbon fiber to base material, increase the boundary strength between carbon fiber and the base material thus, can carry out surface modification to carbon fiber.Surface modification is surface oxidation preferably.The surface oxidation of carbon fiber for example carries out through following technology: carbon fiber is heated in the presence of oxidizing gas; Carbon fiber is immersed in the oxidation liquid, or the carbon fiber that will flood thus heating.From viewpoint easily, preferably, surface oxidation carries out through carbon fiber is heated in air under 300-800 ℃.
The carbon fiber of vapor phase growth of the present invention shows excellent characteristic, for example high conductivity and thermal conductivity.Therefore, when this carbon fiber is sneaked into base material, for example in resin, metal or the ceramic material, when preparing composite thus, the composite of gained shows the characteristic of improving, for example high conductivity and thermal conductivity.Especially; Carbon fiber is being added under the situation of resin with the preparation composite; Even 1/2 (based on quality)-1/3 or lower of the amount of the carbon fiber that the amount of the carbon fiber that is added is a conventional gas-phase grows, this composite still shows the suitable electric conductivity of composite with the carbon fiber that comprises the conventional gas-phase growth; That is, the carbon fiber of vapor phase growth of the present invention has excellent effect.
Particularly, be used in the carbon fiber that resin/carbon fibre composite in anti-static material etc. generally need add 5-15 quality %, to obtain desirable characteristic, electric conductivity for example.On the contrary, only the carbon fiber of a small amount of (the 2-8 quality %) vapor phase growth of the present invention of interpolation just reaches this desirable characteristic.Simultaneously, the carbon fiber with vapor phase growth of the present invention adds the fracture strength that can strengthen the gained composite in the metal to.
The resin base material that carbon fiber of the present invention is dispersed in wherein can be thermoplastic resin or thermosetting resin.The instance of resin base material comprises polyethylene (PE); Polypropylene; Nylon; Polyurethane; Polyacetals; Polyphenylene sulfide; Polystyrene; Merlon; Polyphenylene oxide; PETG; Polybutylene terephthalate (PBT); Polyarylate; Polysulfones; Polyether sulfone; Polyimides; The polyoxy benzoyl; Polyether-ether-ketone; PEI; Teflon (registration mark); Contain silicones; The cellulose acetate resin; ABS resin; The AES resin; The ABMS resin; AAS resin; Phenol resin; Carbamide resin; Melmac; Xylene resin; Diallyl phthalate ester resin; Epoxy resin; Anline resin and furane resins.
The instance of ceramic base material comprises aluminium oxide, mullite, silica, zirconia, carborundum and silicon nitride.
The instance of metal base comprises gold, silver, aluminium, iron, magnesium, lead, copper, tungsten, titanium, niobium, hafnium, its alloy and its mixture.
Embodiment
Through embodiment the present invention is described in more detail below, but these embodiment should not to be regarded as be limitation of the present invention.
Embodiment 1
Use the device of representing in Fig. 1 flow chart, the carbon fiber of preparation vapor phase growth.
Use have at its top the nozzle unit of the gas that is used to supply raw material vertical heating furnace (internal diameter: 370mm, long: 2000mm) as reaction tube (5).
With the adjustment to 500 of gasifier (3) ℃.Make nitrogen pass through reaction system, thus the oxygen in the scavenge system.Then, make hydrogen pass through system, thereby be full of this system with hydrogen.After this, the temperature with reaction tube rises to 1250 ℃.(30g/min) adds gasifier with pump with liquid charging stock, the reaction beginning.Use the raw material that hydrogen (50L/min) will gasify as carrier gas thus to send in the pipeline.Unstrpped gas is being sent into before the reaction tube, used static mixer (4) that it is further mixed with hydrogen (400L/min).Liquid charging stock makes through ferrocene (0.5kg) and thiophene (0.13kg) are dissolved in the benzene (14kg).The content of ferrocene and thiophene is respectively 3.5 quality % and 0.9 quality % in the liquid charging stock.
This reaction was carried out 1 hour under these conditions, thereby generated gas-phase growth of carbon fibre.
The gained carbon fiber was heated 30 minutes in argon atmospher under 2800 ℃, thereby generate the aim carbon fiber.
The carbon fiber of preparation has 0.012g/cm thus 3Bulk density.When this carbon fiber being compressed to bulk density is 0.8g/cm 3The time, it shows the resistivity of 0.007 Ω cm.Under SEM, observe 100 carbon fiber wires, calculate fiber diameter and average fiber length.As a result, fiber diameter is that (standard deviation: 23.4nm), average fiber length is that (average aspect ratio is 13 μ m: 130) to 96.9nm.Fig. 3 representes the fiber diameter distribution profile of carbon fiber.Fibre diameter drops on ± 75% (is benchmark with the radical) that carbon fiber wire in the 20% fiber diameter scope accounts for all carbon fiber wires.Carbonation rate (that is the quality of the quality/benzene feed of prepared carbon fiber) is 50%.
Through raman scattering spectrum, this carbon fiber shows 0.16 Id/Ig.X-ray diffraction is measured the result and is shown that this carbon fiber has the d of 0.338nm 002
Embodiment 2:
Use the unidirectional double screw extruder (Ikegai, the product of Ltd) of φ 30mm, the carbon fiber of the vapor phase growth of the embodiment 1 preparation difference amount with 5-15 quality % is dispersed in the Merlon, thereby prepares different carbon fiber/polycarbonate composite materials.The preparation rate adaptation is to 3kg/h.Through 75-t injection-molding apparatus (product of FANUC LTD) with every kind thus the preparation composite molded one-tenth plate (100mm * 100mm * 2mm is thick).Measure the specific insulation of this plate through four probe method.The result is shown among Fig. 2.
Embodiment 3:
It is 0.1g/cm that the carbon fiber of the vapor phase growth of preparation among the embodiment 1 is compressed into density 3, the fiber that utilizes sliding wear to compress is thus then milled, and is 0.04g/cm thereby obtain bulk density 3Carbon fiber.Use the unidirectional double screw extruder (Ikegai, the product of Ltd) of φ 30mm, the amount of gained carbon fiber with 5 quality % is dispersed in the Merlon, thus preparation carbon fiber/polycarbonate composite material.The preparation rate adaptation is to 10kg/h.The composite of preparation thus is molded as plate (100mm * 100mm * 2mm is thick) through 75-t injection-molding apparatus (product of FANUC).Through the specific insulation of this plate of four probe method measurement, the result is 1 * 10 2Ω cm.
Embodiment 4:
Utilize the device shown in the flow chart of Fig. 1 to prepare gas-phase growth of carbon fibre.
Be employed in the vertical heating furnace (internal diameter: 370mm that its top has the nozzle unit of the gas that is used to supply raw material; Long: 2000mm) as reaction tube (5).
With the adjustment to 500 of gasifier (3) ℃.Make nitrogen pass through reaction system, thus the oxygen in the scavenge system.Then, make hydrogen pass through system, thereby make hydrogen be full of this system.After this, the temperature with reaction tube rises to 1250 ℃.Through liquid charging stock (100g/min) is added in the gasifier reaction beginning with pump.The raw material that will gasify thus through the hydrogen (50L/min) as carrier gas adds in the pipeline.Unstrpped gas is being added before the reaction tube, it is further being mixed with hydrogen (540L/min) through static mixer (4).Liquid charging stock makes through ferrocene (0.5kg) and thiophene (0.13kg) are dissolved in the benzene (14kg).The content of ferrocene and thiophene is respectively 3.5 quality % and 0.9 quality % in the liquid charging stock.
This reaction was carried out 1 hour under these conditions, thus the preparation gas-phase growth of carbon fibre.
The gained carbon fiber was heated 30 minutes in argon atmospher under 2800 ℃, thus preparation aim carbon fiber.
The carbon fiber of preparation has 0.015g/cm thus 3Bulk density.When this carbon fiber being compressed to bulk density is 0.8g/cm 3The time, it shows the resistivity of 0.008 Ω cm.
Under SEM, observe 100 carbon fiber wires, calculate fiber diameter and average fiber length.As a result, fiber diameter is that (standard deviation: 24.1nm), average fiber length is that (average aspect ratio is 10 μ m: 120) to 93nm.Fig. 5 representes the fiber diameter distribution profile of carbon fiber.Fibre diameter drops on ± 73% (is benchmark with the radical) that carbon fiber wire in the 20% fiber diameter scope accounts for all carbon fiber wires.Carbonation rate (that is the quality of the quality/benzene feed of prepared carbon fiber) is 50%.
Through raman scattering spectrum, this carbon fiber shows 0.17 Id/Ig.X-ray diffraction is measured the result and is shown that this carbon fiber has 0.338 d 002
Comparative Examples 1:
Be employed in the vertical heating furnace (internal diameter: 370mm that its top has the two-fluid hollow taper nozzle unit of the gas that is used to supply raw material; Long: 2000mm) as reaction tube.Make nitrogen pass through reaction system, thus the oxygen in the scavenge system.Then, make hydrogen pass through system, thereby make hydrogen be full of this system.After this, the temperature with reaction tube rises to 1250 ℃.With pump liquid charging stock (130g/min) and hydrogen (20L/min) are added through nozzle unit, and hydrogen (400L/min) is added through the flange that is positioned at reaction tube top, thereby reaction is carried out.Liquid charging stock is sprayed onto the inwall of reaction tube.Liquid charging stock makes through ferrocene (0.83kg) and sulphur (0.059kg) are dissolved in the benzene (14kg).The content of ferrocene and sulphur is respectively 5.5 quality % and 0.39 quality % in the liquid charging stock.
This reaction was carried out 1 hour under these conditions, thus the preparation gas-phase growth of carbon fibre.The carbon fiber of preparation has 0.04g/cm thus 3Bulk density.When this carbon fiber being compressed to bulk density is 0.8g/cm 3The time, it shows the resistivity of 0.03 Ω cm.
The carbon fiber for preparing thus at electron microscope observation.As a result, fiber diameter is that (standard deviation: 37.4nm), average fiber length is that (average aspect ratio is 7 μ m: 47) to about 180nm.Fig. 4 representes the fiber diameter distribution profile of carbon fiber.Fibre diameter drops on ± 60% (is benchmark with the radical) that carbon fiber wire in the 20% fiber diameter scope accounts for all carbon fiber wires.Carbonation rate (that is the quality of the quality/benzene feed of prepared carbon fiber) is 60%.
Through raman scattering spectrum, this carbon fiber shows 0.23 Id/Ig.X-ray diffraction is measured the result and is shown that this carbon fiber has 0.340 d 002
Comparative Examples 2:
The carbon fiber of vapor phase growth of preparation in the Comparative Examples 1 was cured under 1000 ℃ 15 minutes, then 2800 ℃ of following graphitizations 15 minutes.Use the unidirectional double screw extruder (Ikegai, the product of Ltd) of φ 30mm, the difference amount of gained carbon fiber with 5-20 quality % is dispersed in the Merlon, thereby prepares different carbon fiber/polycarbonate composite materials.With every kind of composite molded one-tenth goods of preparation thus, and measure the specific insulation of this mechanograph through four probe method through hot pressing.The result is shown among Fig. 2.
Can find out that by Fig. 2 under the situation of sneaking into 5 quality % gas-phase growth of carbon fibre, the specific insulation of the composite of Comparative Examples 2 is about 1.0 * 10 16Ω cm, and the specific insulation of the composite of embodiment 2 is 1.0 * 10 2Ω cm or lower.Simultaneously, under the situation of the composite of embodiment 2, reach about 1.0 * 10 2The amount of the gas-phase growth of carbon fibre that the specific insulation of Ω cm is required is 5 quality %; This consumption is 1/4 of the composite of Comparative Examples 2 amount (that is about 20 quality %) that reaches the required gas-phase growth of carbon fibre of this specific insulation.Therefore; Under the situation that composite is made by the gas-phase growth of carbon fibre of embodiment; Even when the addition of carbon fiber less than the gas-phase growth of carbon fibre of Comparative Examples (promptly; Traditional gas-phase growth of carbon fibre) addition, the electric conductivity of this composite etc. are suitable with the composite that comprises the conventional gas-phase grown carbon fiber.
Industrial applicability:
Preparation in accordance with the present invention, through will be by carbon source, be sprayed onto the inwall of reactor, the carbon fiber that can obtain having special fiber filament diameter and specific draw ratio as the transistion metal compound of catalyst.
And, when carbon fiber and resin are processed composite,, still can give composite excellent electric conductivity and thermal conductivity even addition generates the addition of fiber far below conventional gas-phase.

Claims (7)

1. the carbon fiber of a vapor phase growth, it has draw ratio and the 0.02g/cm of 100-200 3Or lower bulk density, wherein fibre diameter drop on ± carbon fiber wire in the 20% fiber diameter scope account for based on radical whole of said carbon fiber 65% or more.
2. the carbon fiber of vapor phase growth as claimed in claim 1 wherein ought be compressed to 0.8g/cm with the carbon fiber of said vapor phase growth 3Bulk density the time, said carbon fiber shows 0.015 Ω cm or lower resistivity.
3. as the carbon fiber of above-mentioned claim 1 or 2 described vapor phase growths, it shows 0.2 or lower Id/Ig ratio, and wherein Id is illustrated in 1341-1360cm in the raman scattering spectrum of said carbon fiber -1The peak height of wave band d line, Ig is illustrated in 1570-1580cm in the said spectrum -1The peak height of wave band g line.
4. according to claim 1 or claim 2 the carbon fiber of vapor phase growth wherein has 0.339nm or littler centre plane spacing d through the carbon fiber that the X-ray diffraction determination method records said vapor phase growth at (002) mask 002
5. according to claim 1 or claim 2 the carbon fiber of vapor phase growth, the peroxidating of its surface is handled.
6. assembled the carbon fiber of formed vapor phase growth by each described carbon fiber among the claim 1-5, it has 0.04g/cm 3Or higher bulk density.
7. method for preparing the carbon fiber of vapor phase growth according to claim 1; Wherein carrier gas is mixed with the unstrpped gas that comprises carbon source and transistion metal compound; Make that the amount of said carrier gas is 1-100mol based on the 1mol organic compound as said carbon source, subsequently the gained admixture of gas is sent into reactor.
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